Liquid octa 2-lower alkoxy ethoxides of aluminum and (magnesium or calcium)

ABSTRACT

Alkoxy ethoxides, for example 2-methoxy ethoxide, of aluminum and magnesium or aluminum and calcium, are provided. These compounds are of the formula MAl2(O-CH2-CH2-O-R)8 wherein M is calcium or magnesium and wherein R is an alkyl of 1 to 4 carbon atoms; they are liquids at about 25*C. and about 1 atmosphere of pressure and are produced by reacting aluminum and magnesium or calcium with mono-alkyl ethers of ethylene glycol. Methods for hydrolyzing the compounds to obtain oxides of the formula MgAl2O4 and CaAl2O4 are disclosed. For example, magnesium aluminum octa(2 methoxy ethoxide) is produced, using ethylene glycol monomethyl ether (methyl &#39;&#39;&#39;&#39;Cellosolve&#39;&#39;&#39;&#39;) as a reagent; the material is hydrolyzed and heated to form MgAl2O4.

United States Patent 1 1 Thomas 1 Sept. 2, 1975 LIQUID OCTA 2-LOWERALKOXY ETI-IOXIDES OF ALUMINUM AND (MAGNESIUM OR CALCIUM) Ian M. Thomas,Temperance, Mich.

[52] US. Cl. 260/448 AD; 423/600' [51] Int. Cl. C07f 5/06 [58] Field ofSearch 260/448 AD [56] References Cited UNITED STATES PATENTS 1,689,35610/1928 Meerwein 260/448 AD 2,570,058 10/1951 Hunter 260/632 X 2,593,3144/1952 Kimberlin 252/475 X 2,687,423 8/1954 Mesirow 260/448 AD 2,776,188l/l957 Gilbert 252/475 X 2,805,167 9/1957 McCreight et a1 423/6002,917,366 12/1959 Hansford 260/448 AD X 3,060,216 10/1962 Hamprecht eta1. 260/448 AD 3,304,153 2/1967 Bakker et a1. 106/62 X 3,394,158 7/1968Chini et a1. 260/448 AD 3,413,083 11/1968 Daendliker 423/600 3,488,3701/1970 Leary et a1 260/448 AD 3,507,895 4/1970 Casensky et a1. 260/448AD 3,510,272 5/1970 Schmank 423/600 3,565,646 2/1971 Housh 106/653,631,083 12/1971 Hartmann 260/448 AD 3,637,406 l/l972 Bailey 106/65 X3,639,664 1/1972 Schmank et al. 260/448 AD 3,657,361 4/1972 Lenz et a1.260/615 R 3,761,500 9/1973 Thomas 260/448 AD 3,773,733 1 H1973Matsushima 260/448 AD X OTHER PUBLICATIONS Chemical Abstracts, Vol. 24,pp. 586587, (1930). Chemical Abstracts, Vol. 37, p. 5020, (1943).

Primary Examiner-Helen M. S. Sneed Attorney, Agent, or Firm-Robert F.Rywalski; Edward .1. Holler [57] ABSTRACT Alkoxy ethoxides, for example2-methoxy ethoxide, of aluminum and magnesium or aluminum and calcium,are provided. These compounds are of the formula MAl (O-CH -CH O R)wherein M is calcium or magnesium and wherein R is an alkyl of 1 to 4carbon atoms; they are liquids at about 25C. and about I atmosphere ofpressure and are produced by reacting aluminum and magnesium or calciumwith mono-alky1 ethers of ethylene glycol. Methods for hydrolyzing thecompounds to obtain oxides of the formula MgA1 O and CaAl O aredisclosed. For example, magnesium aluminum octa-(2 methoxy ethoxide) isproduced, using ethylene glycol monomethyl ether (methyl Cellosolve) asa reagent; the material is hydrolyzed and heated to form MgA1 O,.

11 Claims, No Drawings THE INVENTION This invention relates tocompositions containing aluminum and magnesium, or calcium, and moreparticularly it relates to magnesium-aluminum or calcium aluminumocta-[2 alkoxy ethoxides] of the formula l to 4 carbon atoms and M ismagnesium or calcium.

U.S. Pat. No. 3,510,272 discloses the hydrolysis of magnesium aluminumisopropoxide, or isopropylate, and other calcium aluminum alcoholatesand magnesium aluminum alcoholates wherein the alcoholate or alkoxidegroup contains 2 to 5 carbon atoms. US. Pat. No. 3,413,083 discloses theproduction of mixed oxides by the use of separate alcoholates ofdifferent metals. This patent also indicates the formation of bariumtitanate by hydrolysis and calcination of BaTi(OR),,. U.S. Pat. No.3,637,406 claims that aluminum isopropoxide and magnesium isopropoxideare sources of alumina and magnesia respectively. It is also known thatmagnesia spinel can be formed when the sources of magnesia and aluminaare magnesium hydroxide, or hydrate, and aluminum hydroxide, or hydrate.See, for example, US. Pat. No. 3,304,153, US. Pat. No. 2,805,167, andUS. Pat. No. 3,565,646. US. Pat. Nos. 2,593,314 and 2,570,058 disclosethe production of hydrated magnesia from certain magnesium alcoholates.US. Pat. No. 2,776,188 discloses a process for forming metal oxide gelsby spraying hydrolyzable metal compounds into an atmosphere of steam orwater vapor; the hydrolyzable metal compounds include aluminumalcoholates, phenolates and cresylates of aluminum, magnesium, zinc,titanium, calcium, chromium, manganese, etc., or alloys thereof. US.Pat. No. 1,689,356 discloses techniques for forming complex alcoholatessuch as, for example, magnesium aluminum ethylate. US. Pat. No.2,917,366 discloses the reaction of aluminum trialkoxides withpolyhydric alcohols to form a polymeric specie which is then convertedto alumina. US. Pat. NO. 3,631,083 discloses the reaction of Mg(OR) andAl- (OR) wherein R is alkyl to C and polyhydroxy compounds in thepresence of water to form complexes thereof. US. Pat. No. 3,657,361discloses the forma tion of compounds of the formula Mg(OR) .(ROH),,wherein n is a number from 0 to 3, preferably 0 or 3, and R is an alkylradical having 1 to 3 carbon atoms or a radical of the general formula R-O---R wherein R is an alkylene radical and R is an alkyl radical with Rand R having a total of 3 to 4 carbon atoms; various activators such asorthoformic acid esters, p-toluene sulfonic acid, iodine, halogens andother materials are disclosed whereby the reaction is effected.

Thus, from the foregoing, it will be seen that none of the above patentsdiscloses the formation of aluminum and magnesium or aluminum andcalcium octa-[2 lower alkoxy ethoxides[, nor do they disclose that thesecompounds are liquids at about 25 C. and l atmosphere of pressure.Similarly, none of these references discloses that these compounds canbe formed by reacting aluminum and magnesium, or calcium, with monolower alkyl ethers of ethylene glycol to form these compounds or thatthe compounds can be hydrolyzed to form high purity, substantiallyanhydrous, amorphous oxide compositions corresponding to the formulaMgAI- O, or CaAl-,O or the crystalline forms, i.e., magnesium or calciumspinels.

Thus, in accordance with one aspect of this invention, there areprovided, as compositions of matter, compounds which are liquid at about25 C. and about 1 atmosphere of pressure wherein the compounds are ofthe formula MA/ (O-CH --CH -O-R) wherein M is calcium or magnesium and Ris a C to C alkyl, such as, for example, methyl, ethyl or normal butyl.The liquid nature of these products allows them to be more convenientlyhandled than solid aluminum and magnesium, or aluminum and calcium,alcoholates. The present materials are also easily distilled to producehighly pure products.

In accordance with another feature of this invention, MAl (O--CH -CI-I-O-R) compounds, as described above, are produced by heating, betweenabout ambient temperature and reflux, but preferably at reflux, calciumor magnesium and aluminum and a compound of the formula ROCH CH O-I-Iwherein R is a C to C alkyl so as to effect reaction and formation ofthe desired compounds, which compounds are then separated from thereaction mass, e.g., by distillation. The reaction will typically beconducted to substantial completion and it is found that quite desirablereaction rates are obtained. In contrast to magnesium, or calcium,aluminum alkoxides or alcoholates, wherein the alkoxide or alcoholategroup is a (OR) group supplied by alkyl alcohols (ROH), it will be foundthat the present reaction will typically proceed at a rate slightlyslower than the rate obtained when normal alkyl alcohols are employedbut at a rate significantly faster than when secondary alkyl alcoholsare used and even more substantially at a faster rate when contraster totertiary alkyl alcohols. The alcoholates formed with normal alkylalcohols are solid alkoxides of aluminum and calcium or magnesium. Thus,the present invention allows for the production of liquid compoundswhich, as indicated previously, are much more convenient for utilizationthan solids. When the alcoholates are formed from certain secondaryalkyl alcohols, liquid products are produced; the present invention,however, has the advantage that the process for the formation of theliquid compounds involved herein proceeds at a substantially faster ratethan when secondary alkyl alcohols are employed as reagents. Thus,liquid products can be produced in a more economical manner with muchfaster reaction rates. When tertiary lower alkyl alcohols are employedto form alcoholates or alkoxides, the reactions are extremely long andimpractical; thus, the present invention has a superior advantage inthat it is a much shorter reaction.

In the preferred manner of practicing the invention, magnesium (orcalcium) and aluminum are reacted with a compound of the formula ROCHCl-l- OH at the reflux temperature of the system. This is done byheating the reaction mass and maintaining the reflux condition until thereaction is substantially complete. It will also be found that thereaction rate is sufficient so that there is no need to employ anyreaction promoters to obtain desirable rates. That is, the method can bepracticed in the absence of catalysts or activators. Preferably, thereaction is conducted with an excess of the stoichiometric amount(hereinafter also referred to as stoichiometric excess) of the compoundof the formula RO-CH CH OI-I and quite convenient proportions will befound to be in excess of about 4 to about 8 moles of said compound pergram atom of aluminum employed. Aluminum 2-lower alkoxy ethoxides aresomewhat similar in volatility to the calcium (or magnesium) aluminumocta (2-lower alkoxy ethoxides), thereby making separation difficult;magnesium (or calcium) 2-lower alkoxy ethoxides are much less volatilethan the aluminum and magnesium (or calcium) compounds, thereby allowingthe latter compounds to be easily separated from the former if present.Consequently, it will be desirable to use a stoichiometric amount ofslight deficiency of aluminum relative to the calcium or magnesium.Thus, suitable proportions would be about 2 gram atoms of aluminum pergram atom of calcium (or magnesium), or less, for example about 1.9 toabout 2 moles of aluminum per gram atom of magnesium or calcium, withquite excellent results being obtained using a ratio of about 1.95 toabout 2: l for example 1.97. Stoichiometric amounts for the reaction are1 gram atom of Mg or Ca, 2 gram atoms of Al and 8 moles of ROCH CH OH.After the reaction has gone to substantial completion, there will remaina solution of the MAl (OCl-I CH- ,,-O-R) compound in the excess of theROCl-l- CH -OH compound. Following conventional techniques, the excessof the latter material will be removed, for example, by volatilizationor distillation and then the desired compound will be separated from theresidual material, preferably by distilling it off. Usually, it will beconvenient to use high vacuums for the volatilization, such as, forexample, pressures of about 1 millimeter of mercury or less.

The compounds of the formula MAI (OCH CH- -OR),,, wherein M is calciumor magnesium and R is a C,C alkyl, are hydrolyzable compounds andconsequently are convenient sources for the production of compounds ofthe formula MgAl- O or CaAl Q that is, the spinels. Thus, in accordancewith another feature of this invention, the aluminum and calcium ormagnesium octa [2-lower alkoxy ethoxides] are added to a non-polarorganic solvent, such as, for example, higher alkanes, like heptane, oraromatic compounds, like benzene, so as to form a solution and then thissolution is combined with water so as to hydrolyze the compound and forma hydrolyzed precipitate. For quantitative conversions to the hydrolyzedprecipitate, at least about 6 moles of water will be employed per moleof the aluminum and calcium or magnesium octa [2-lower alkoxy ethoxide]compound. Usually, amounts of water in excess of this amount, forexample, the theoretical stoichiometric amount of about 8 moles ofwater, will be employed or for that matter, excesses can be used up to10 moles of water or even more. After the hydro lyzed precipitate isformed, the volatiles which will include the solvent employed and alsothe by-product 2- alkoxy ethanols, are separated, for example byfiltration, leaving as a residue the hydrolyzed precipitate. Thisprecipitate is then typically dried to a particulate mass such as, forexample, by heating at lOO to 120 or 130 C or even higher for a time todry same and then it is further heated to form an anhydrous, amorphous,small particle size, high surface area, high purity oxide product. Thefurther heating of the dried product will typically be done at atemperature and for a time sufficient to remove residual carbonmoieties, which carbon moieties may be present in the form of boundreaction product, residual 2-alkoxy ethoxide groups, which latter groupsmay be present notwithstanding the fact that more than a stoichiometricamount of the water needed for full hydrolysis is employed, or evenbound solvent; the heating will generally be done at a temperature lessthan about 700 C. so as to form a white, carbon free, anhydrous,amorphous, small particle size, high surface area, high purity oxideproduct.

Typically, for example, as the dried, hydrolyzed prod-' uct is heated,it will convert to a somewhat brownish colored material and attemperatures of about 400 C. it will convert to a substantially whitecolored particulate mass. Thus, for example, convenient temperatures tobe employed to remove residual carbon moieties will be temperatures onthe order of about 400 C. to less than about 700 C. for example, about400 to 500 C. This resulting anhydrous, amorphous composition is of anextremely small particle size, typically having particles of the size ofabout to 200 angstroms, has a surface area of about 300400 square metersper gram and an extremely high purity level. For example, when usingfreshly distilled compounds of the formula MAl (OCH -Cl-l O-R) and highpurity water, for example, distilled, impurity levels of about 50 partsper million or less of total other metal oxides are typically obtained,with no other single metal oxide being present in an amount greater thanabout 10 ppm by weight. These anhydrous, amorphous, small particle size,high surface area, high purity oxide products are excellent supports forcatalytic polymerization of olefins, especially polyethylene.

In order to convert the anhydrous, amorphous, small particle size, highsurface area, high purity oxide product into a high purity, crystallinecomposition corresponding to the formula MgAI O or CaAl O,,, all that isneeded is to further heat the former product at a temperature and for atime sufficient to effect the crystallization of the material. Thus, forexample, the amorphous product can be consolidated or compacted into asolid unitary body, using conventional cold or hot pressing techniquesand subjected to temperatures and times sufficient to convert theproduct to a crystalline, consolidated body of the formula CaAl O orMgAl' O or, if desired, the particulate amorphous product, without beingcompacted or consolidated, can be so heated. It has been found that atemperature in excess of about 700 C. will be needed to effectconversions to the crystalline material.

While the foregoing generally describes hydrolysis wherein the productsof the formula MAl (OCl-l- Cl-l O-R) were separated from the reactionmass in which they were formed and then added to another solvent andthen hydrolyzed, this procedure may be varied. That is, according toanother feature of this invention, magnesium or calcium and aluminum arereacted with a stoichiometric excess of a compound of the formula ROCHCH OH, preferably at the reflux temperature of the reaction mass, for atime sufficient to form a compound of the formula MAl (OCH- CH OR),, andthen this reaction mass, which will be a solution, is combined andcontacted with water as described above so as to precipitate ahydrolyzed product and then the hydrolyzed product is dried, that is,separated from the bulls of the volatiles and then heated in the mannerindicated above to form either anhydrous, amorphous, particulateproducts or heated still more to form either consolidated or particulatecrystalline products of the formula CaAI- O, or MgAl- "O While theinvention has been described above with sufficient particularity toenable those skilled in the art to make and use same without an undueamount of experimentation and has indicated some of the best modescontemplated in practicing this invention, several examples follow.These examples are not to be construed as limiting and are set forth tofurther enable those skilled in the art to make and use the presentinvention.

EXAMPLE 1 According to the following procedure, magnesium aluminumocta-(2-methoxy ethoxide) is produced by using the monomethyl ether ofethylene glycol as a reagent. lnto a reaction flask there are addedabout 250 grams of methyl Cellosolve and the reaction flask is equippedwith a conventional soxhlet extractor. The thimble of the soxhletextractor is previously charged with about 6.1 grams of magnesiumturnings and about 13.5 grams of aluminum wire. The methyl Cellosolve isheated to reflux with stirring and a vigorous reaction soon starts withall of the magnesium being consumed in about minutes and the aluminum inan additional 90 minutes to produce a fluid product which is a solutionof the magnesium aluminum octa (2-methoxy ethoxide) in the excess methylCellosolve. The fluid product is then evaporated under vacuum to removeexcess methyl Cellosolve and the liquid residue, which is the magnesiumaluminum octa (2-methoxy ethoxide is thereafter distilled from thereaction flask under vacuum (about 0.1 mm of mercury pressure and at atemperature of about 240 to 245 C.). The product is a pale yellow liquidand is obtained in about 90 percent yield.

About 150 grams of the distilled product are dissolved in about 800 ccof benzene to form a solution and the solution is then combined withdistilled water to effect hydrolysis, the amount of water being about 8moles of water per mole of product employed. A hydrated oxideprecipitate is formed and is separated from the solution by filtration.The precipitate is then heated at about 120 C. for a time sufficient toevaporate the solvent and produce a dry particulate product; the driedproduct is further heated to remove residual carbon moieties. Attemperatures between about 250300 C. and up to a temperature of about400 C. the material is somewhat brown but at a temperature of about 400C. it converts to a white, carbon free, anhydrous product. This producttypically has particle sizes in the range of about 100 to 200 angstromsand a surface area typically of about 300-400 square meters per gram andtypically contains less than about 50 parts per million totalimpurities. This product is amorphous and represents an excellentcatalyst support for the production of olefin polymers and especiallythe production of polyethylene.

A portion of the particulate amorphous white material as produced aboveis then heated to a temperature of about 1200 C and an analysis of theparticulate product after heating to 1200 C shows a compositiongenerally corresponding to a molar ratio of MgO:Al O;, of about1.00:1.02, whereas the theoretical value for spinel (MgAl- O or MgO.AlO;,) is 1:1. High quality, pure crystalline spinel bodies are easilyformed using conventional techniques, such as compaction by means ofpressing, wherein the material which is compacted is the amorphousparticulate material described above and the compact then heated at atemperature and for a time sufficient to form a crystalline body.Typically it will be found that the amorphous product converts tocrystalline spinel at a temperature of about 700 C.

EXAMPLE 2 Substantially similar results are obtained when practicing theprocedure of Example 1 to produce magnesium aluminum octa (2-ethoxyethoxide) using ethyl Cellosolve and magnesium aluminum octa (2-normalbutoxy ethoxide) using n-butyl Cellosolve.

EXAMPLE 3 Following the general procedure of Example I, calcium aluminumocta (2-methoxy ethoxide) is produced using a ratio of about 1.97 gramatoms of aluminum per gram atom of calcium and about 6.5 moles of methylCellosolve per gram atom of aluminum. The liquid product is separatedfrom the reaction medium in about a 96 percent yield at a boiling pointof about 220 to 230 C. at a pressure of about 0.1 mm of mercury. Theproduct is shown by analysis to be CaAl (O-CH- CH OCH When hydrolyzed asindicated in the manner set forth in Example 1, substantially similarresults are obtained.

EXAMPLE 4 The general procedure of Example 1 is repeated using about1.97 gram atoms of aluminum per gram atom of magnesium and about 6.5moles of methyl Cellosolve per gram atom of aluminum but the excessCellosolve and the resultant magnesium aluminum octa (2- methoxyethoxide) is not separated after the synthesis reaction. Instead, thesolution containing the MgAl (O-CH -CH OCH product in excess methylCellosolve is combined with about 8 moles of water to hydrolyze themagnesium-aluminum product, producing a hydrated oxide precipitate. Thisprecipitate is then treated in the manner indicated in Example 1 withsubstantially similar results being obtained except the purity level maybe lower. Higher purity levels are obtainable by using higher puritymetals. 34

I claim:

1. As a composition of matter, a compound which is liquid at about 25 C.and about 1 atmosphere of pressure, said compound being of the formulaMAl (OCH CH OR) wherein M is Ca or Mg and R is a C,--C alkyl.

2. The composition of claim 1 wherein M is Ca.

3. The composition of claim 2 wherein R is methyl.

4. The composition of claim 1 wherein M is Mg.

5. The composition of claim 4 wherein R is methyl.

6. The composition of claim 4 wherein R is ethyl.

7. The composition of claim 4 wherein R is normal butyl.

8. The method for making a compound which is liquid at about 25C. andabout 1 atmosphere of pressure wherein said compound is of the formulaMAI- (OCH- CH -OR) wherein M is calcium or magnesium and R is a C Calkyl, comprising the steps of heating Mg or Ca and Al and a compound ofthe formula ROCH CH ,--OH wherein R is described as above. and whereinthe ratio of the gram atoms of aluminum to magnesium or calcium is about2:1 or less and wherein said ROCH CH -O-H compound is present in anamount in excess of the stoichiometric amount, for a period of timesufficient to moved from the reaction mass prior to separation of saidMAl- (OCH -CH OR) compound.

10. The method of claim 9 wherein the ratio of the gram atoms ofaluminum to magnesium is between about 1.9 to about 2:1.

11. The method of claim 10 wherein the ratio of the number of moles ofsaid ROCH CH OH compound to the gram atoms of Al is in excess of about 4to about 8:1.

1. As a composition of matter, a compound which is liquid at about 25*C. and about 1 atmosphere of pressure, said compound being of theformula MAl2(O-CH2-CH2-O-R)8 wherein M is Ca or Mg and R is a C1-C4alkyl.
 2. The composition of claim 1 wherein M is Ca.
 3. The compositionof claim 2 wherein R is methyl.
 4. The composition of claim 1 wherein Mis Mg.
 5. The composition of claim 4 wherein R is methyl.
 6. Thecomposition of claim 4 wherein R is ethyl.
 7. The composition of claim 4wherein R is normal butyl.
 8. THE METHOD FOR MAKING A COMPOUND WHICH ISLIQUID AT ABOUT 25*C AND ABOUT 1 ATMOSPHERE OF PRESSURE WHEREIN SAIDCOMPOUND IS OF THE FORMULA MA12(O-CH2-CH2-O-R)8 WHEREIN M IS CALCIUM ORMAGNESIUM AND R IS A C1-C4 ALKYL COMPRISING THE STEPS OF HEATING MG ORCA AND A1 AND A COMPOUND OF THE FORMULA R-O-CH2-CH2-O-H WHEREIN R ISDESCRIBED AS ABOVE AND WHEREIN THE RATIO OF THE GRAM ATOMS OF ALUMINUMTO MAGNESIUM OR CALCIUM IS ABOUT 2:1 OR LESS AND WHEREIN SAIDR-O-CH2-CH2-O-H COMPOUND IS PRESENT IN AN AMOUNT IN EXCESS OF THESTOICHIOMETRIC AMOUNT FOR A PERIOD OF TIME SUFFICIENT TO FORM SAIDMA12(O-CH2-CH2O-R)8 COMPOUND AND SEPARATING SAID MA12(O-CH2-CH, 2-O-R)8COMPOUND FROM THE REACTION MASS.
 9. The method of claim 8 wherein saidexcess is removed from the reaction mass prior to separation of saidMAl2(O-CH2-CH2-OR)8 compound.
 10. The method of claim 9 wherein theratio of the gram atoms of aluminum to magnesium is between about 1.9 toabout 2:1.
 11. The method of claim 10 wherein the ratio of the number ofmoles of said R-O-CH2-CH2-O-H compound to the gram atoms of Al is inexcess of about 4 to about 8:1.